CN114671860B - Purification method of high-content propiconazole - Google Patents
Purification method of high-content propiconazole Download PDFInfo
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- CN114671860B CN114671860B CN202210429391.3A CN202210429391A CN114671860B CN 114671860 B CN114671860 B CN 114671860B CN 202210429391 A CN202210429391 A CN 202210429391A CN 114671860 B CN114671860 B CN 114671860B
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- propiconazole
- toluene
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- purification method
- dilauryl thiodipropionate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a purification method of high-content propiconazole, which comprises the following specific processes: 300kg of propiconazole crude product, 780kg-850kg of toluene, 0.1kg-1.5kg of toluene solution of dilauryl thiodipropionate, 50kg-80kg of water and 1kg-3kg of hydrochloric acid are sequentially added into a reaction kettle; then stirring for 30-70 min at 20-50 ℃; after the reaction is finished, layering is carried out, and an upper organic phase is obtained through separation; and removing toluene in the upper organic phase by distillation under normal pressure and then reduced pressure, and continuing to distill to obtain propiconazole. The purification method of the high-content propiconazole has the advantages of high yield, less time consumption, convenient operation and high purity of the prepared product.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a purification method of high-content propiconazole.
Background
Propiconazole is a systemic triazole systemic bactericide with protective and therapeutic effects, can be absorbed by roots, stems and leaves, is quickly conducted upwards in plants, is used for preventing and treating diseases caused by ascomycetes, basidiomycetes and fungi imperfecti, and has good prevention and treatment effects on rice blast, false smut, banded sclerotial blight, bakanae disease, wheat take-all, powdery mildew, rust, root rot, banana leaf spot and the like.
The synthesis of propiconazole generally comprises three methods, namely a bromination method, a chlorination method and a post cyclization method, and at present, 2, 4-dichloroacetophenone is mainly used as a raw material, is firstly brominated, is then cyclized with 1, 2-pentanediol, and is finally condensed with 1,2, 4-triazole sodium to generate the propiconazole, so that the synthesis process is most widely used. When propiconazole is prepared by the synthetic process of propiconazole, partial oxidation can occur during high vacuum rectification, so that propiconazole changes color, generally has deep color, is basically red and slightly turbid, influences the product content and refining yield, and is not welcomed by the market.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a purification method of high-content propiconazole.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a purification method of high-content propiconazole comprises the following specific processes:
300kg of propiconazole crude product, 780kg-850kg of toluene, 0.1kg-1.5kg of toluene solution of dilauryl thiodipropionate, 50kg-80kg of water and 1kg-3kg of hydrochloric acid are sequentially added into a reaction kettle; then stirring for 30-70 min at 20-50 ℃; after the reaction is finished, layering is carried out, and an upper organic phase is obtained through separation; and removing toluene in the upper organic phase by distillation under normal pressure and then reduced pressure, and continuing to distill to obtain propiconazole.
Further, the mass content of propiconazole in the propiconazole crude product is 80% -87%.
Further, in the toluene solution of the dilauryl thiodipropionate, the mass ratio of the dilauryl thiodipropionate to toluene is 1:1-2.
Further, the mass concentration of the hydrochloric acid is 20% -30%.
Further, the working condition of decompression is that the temperature is 115-120 ℃ and the pressure is-0.098 MPa to-0.088 MPa.
The invention has the beneficial effects that:
(1) According to the purification method of the high-content propiconazole, disclosed by the invention, the solution prepared by the dilauryl thiodipropionate and toluene is added before the crude propiconazole is rectified, so that the propiconazole product is more stable, free of oxidation and discoloration in the purification process, and better in effect than the effect that the antioxidant protective agent is added only when the propiconazole is rectified by other processes.
(2) The toluene in the solution prepared from the dilauryl thiodipropionate and the toluene can be recycled, and the propiconazole is distilled out by continuous distillation after the toluene is removed, so that the propiconazole with high content, good color and high transparency can be obtained.
(3) The purification method of the high-content propiconazole has the advantages of high yield, less time consumption, convenient operation and high purity of the prepared product.
Detailed Description
The present invention will be further described below, and it should be noted that, while the present embodiment provides a detailed implementation manner and a specific operation process on the premise of the present technical solution, the protection scope of the present invention is not limited to the present embodiment.
Example 1
The embodiment provides a purification method of high-content propiconazole, which comprises the following specific processes:
300kg of crude propiconazole, 780kg of toluene, 0.1kg of dilauryl thiodipropionate toluene solution, 50kg of water and 1kg of 20% hydrochloric acid are sequentially added into a reaction kettle. Then stirred at 20℃for 30min. And after the reaction is finished, layering and separating to obtain an upper organic phase. And distilling the upper organic layer under reduced pressure after normal pressure to remove toluene in the organic layer, and continuing to distill to obtain propiconazole.
The propiconazole content of the crude propiconazole product of this example was 80%. The mass ratio of the dilauryl thiodipropionate to the toluene in the toluene solution of the dilauryl thiodipropionate is 1:1; the pressure reduction working condition is that the temperature is 115 ℃ and the pressure is-0.098 MPa.
Example 2
The embodiment provides a purification method of high-content propiconazole, which comprises the following specific processes:
300kg of propiconazole crude product, 800kg of toluene, 0.2kg of toluene solution of dilauryl thiodipropionate, 60kg of water and 1.5kg of 30% hydrochloric acid are sequentially added into a reaction kettle; then stirred at 30℃for 40min. And after the reaction is finished, layering and separating to obtain an upper organic phase. And distilling the upper organic layer under reduced pressure after normal pressure to remove toluene in the organic layer, and continuing to distill to obtain propiconazole.
The content of propiconazole in the crude propiconazole product is 83%. The mass ratio of the dilauryl thiodipropionate to the toluene in the toluene solution of the dilauryl thiodipropionate is 1:1.5. The pressure reduction working condition is that the temperature is 115 ℃ and the pressure is-0.089 MPa.
Example 3
The embodiment provides a purification method of high-content propiconazole, which comprises the following specific processes:
300kg of propiconazole crude product, 780kg of toluene, 0.3kg of toluene solution of dilauryl thiodipropionate, 50kg of water and 1kg of 20% hydrochloric acid are sequentially added into a reaction kettle; then stirred at 20℃for 30min. And after the reaction is finished, layering and separating to obtain an upper organic phase. And distilling the upper organic layer under reduced pressure after normal pressure to remove toluene in the organic layer, and continuing to distill to obtain propiconazole.
The content of the propiconazole crude product is 83%. The mass ratio of the dilauryl thiodipropionate to the toluene in the toluene solution of the dilauryl thiodipropionate is 1:1. The pressure reduction working condition is that the temperature is 115 ℃ and the pressure is-0.098 MPa.
Example 4
The embodiment provides a purification method of high-content propiconazole, which comprises the following specific processes:
to the reaction vessel were successively added 300kg of crude propiconazole, 830kg of toluene, 1kg of a toluene solution of dilauryl thiodipropionate, 70kg of water and 2.5kg of 30% hydrochloric acid. Then stirred at 40℃for 60min. And after the reaction is finished, layering and separating to obtain an upper organic phase. And distilling the upper organic layer under reduced pressure after normal pressure to remove toluene in the organic layer, and continuing to distill to obtain propiconazole.
The content of propiconazole in the crude propiconazole is 85%. The mass ratio of the dilauryl thiodipropionate to the toluene in the toluene solution of the dilauryl thiodipropionate is 1:1. The pressure reduction working condition is that the temperature is 115 ℃ and the pressure is-0.098 MPa.
Example 5
The embodiment provides a purification method of high-content propiconazole, which comprises the following specific processes:
300kg of crude propiconazole, 850kg of toluene, 1.5kg of a toluene solution of dilauryl thiodipropionate, 80kg of water and 3kg of 30% hydrochloric acid are sequentially added into the reaction kettle. Then stirred at 50℃for 70min. And after the reaction is finished, layering and separating to obtain an upper organic phase. And distilling the upper organic layer under reduced pressure after normal pressure to remove toluene in the organic layer, and continuing to distill to obtain propiconazole.
The content of propiconazole in the crude propiconazole is 87%. The mass ratio of the dilauryl thiodipropionate to the toluene in the toluene solution of the dilauryl thiodipropionate is 1:2. The pressure reduction working condition is that the temperature is 120 ℃ and the pressure is-0.088 MPa.
To determine the performance of the purification process for high propiconazole of each of the above examples, the content, weight and color of propiconazole products prepared in examples 1-5 were measured, and the measurement results are shown in Table 1:
TABLE 1
Various modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing teachings and are intended to be included within the scope of the following claims.
Claims (3)
1. The method for purifying propiconazole is characterized by comprising the following specific steps:
300kg of propiconazole crude product, 780kg-850kg of toluene, 0.1kg-1.5kg of toluene solution of dilauryl thiodipropionate, 50kg-80kg of water and 1kg-3kg of hydrochloric acid are sequentially added into a reaction kettle; then stirring for 30-70 min at 20-50 ℃; after the reaction is finished, layering is carried out, and an upper organic phase is obtained through separation; removing toluene in the upper organic phase by distillation under normal pressure and then reduced pressure, and continuing to distill to obtain propiconazole;
the mass content of propiconazole of the propiconazole crude product is 80% -87%;
in the toluene solution of the dilauryl thiodipropionate, the mass ratio of the dilauryl thiodipropionate to toluene is 1:1-2.
2. The purification method according to claim 1, wherein the mass concentration of the hydrochloric acid is 20% -30%.
3. The purification method according to claim 1, wherein the reduced pressure is operated at a temperature of 115 ℃ to 120 ℃ and a pressure of-0.098 MPa to-0.088 MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210429391.3A CN114671860B (en) | 2022-04-22 | 2022-04-22 | Purification method of high-content propiconazole |
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| CN202210429391.3A CN114671860B (en) | 2022-04-22 | 2022-04-22 | Purification method of high-content propiconazole |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323612A (en) * | 2008-07-14 | 2008-12-17 | 江苏七洲绿色化工股份有限公司 | Preparation of bactericide propiconazole |
| CN102225935A (en) * | 2011-04-27 | 2011-10-26 | 山东潍坊双星农药有限公司 | Manufacturing method of proPiconazole |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323612A (en) * | 2008-07-14 | 2008-12-17 | 江苏七洲绿色化工股份有限公司 | Preparation of bactericide propiconazole |
| CN102225935A (en) * | 2011-04-27 | 2011-10-26 | 山东潍坊双星农药有限公司 | Manufacturing method of proPiconazole |
Non-Patent Citations (1)
| Title |
|---|
| 丙环唑的合成及表征;王珊;郭金婵;夏飞;古元梓;杨光;;应用化工(04);517-519 * |
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